Synthesis and Structure of Carborane-Substituted Cyclic and Polymeric Phosphazenes

Harry R. Allcock, A. G. Scopelianos, J. P. O'Brien, M. Y. Bernheim

Research output: Contribution to journalArticle

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Abstract

The synthesis of the first carborane-substituted cyclophosphazenes together with the preparation, by two different approaches, of the first carborane-substituted phosphazene linear polymers is reported. The cyclic derivatives IV are both precursors and model compounds for the analogous polymeric derivatives VI. The crystal and molecular structure of IV (R = phenyl) has been investigated by single-crystal X-ray diffraction techniques. The molecule contains a planar phosphazene trimer ring bound directly to the phenyl carboranyl group through a P-C bond. The absence of steric and electronic influences by the phosphazene and carboranyl units on each other is discussed. The crystals of IV (R = phenyl) are monoclinic with the space group P21/n and with a = 9.476 (3) Å, b = 12.984 (2) Å, c = 18.726 (3) Å, and β = 100.11 (3)° with V= 2268.2 (3) Å3 and Z = 4. The P-N bond distances are all similar and average 1.574 A. The P-C bond length is 1.820 A. and the Cl-P-C angle was found to be 102.4°. The reaction between high molecular weight poly(dichlorophosphazene), (NPCl2)n, and methyl- or phenyl-1-lithio-o-carborane was also studied. Chlorine substitution is a slow process, and is accompanied by chain cleavage. The nucleophilic replacement of the halogen atoms yielded high polymers of structure IX that contain up to 15% of the side groups as carboranyl units. The remaining chlorine atoms were replaced by treatment with sodium trifluoroethoxide. The properties and structure of the macromolecules are discussed.

Original languageEnglish (US)
Pages (from-to)350-357
Number of pages8
JournalJournal of the American Chemical Society
Volume103
Issue number2
DOIs
StatePublished - Jan 1 1981

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Chlorine
Polymers
Derivatives
Atoms
Halogens
Bond length
Molecular Structure
Macromolecules
X-Ray Diffraction
Molecular structure
Substitution reactions
Crystal structure
Molecular Weight
Sodium
Molecular weight
Single crystals
X ray diffraction
Crystals
Molecules

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Allcock, Harry R. ; Scopelianos, A. G. ; O'Brien, J. P. ; Bernheim, M. Y. / Synthesis and Structure of Carborane-Substituted Cyclic and Polymeric Phosphazenes. In: Journal of the American Chemical Society. 1981 ; Vol. 103, No. 2. pp. 350-357.
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abstract = "The synthesis of the first carborane-substituted cyclophosphazenes together with the preparation, by two different approaches, of the first carborane-substituted phosphazene linear polymers is reported. The cyclic derivatives IV are both precursors and model compounds for the analogous polymeric derivatives VI. The crystal and molecular structure of IV (R = phenyl) has been investigated by single-crystal X-ray diffraction techniques. The molecule contains a planar phosphazene trimer ring bound directly to the phenyl carboranyl group through a P-C bond. The absence of steric and electronic influences by the phosphazene and carboranyl units on each other is discussed. The crystals of IV (R = phenyl) are monoclinic with the space group P21/n and with a = 9.476 (3) {\AA}, b = 12.984 (2) {\AA}, c = 18.726 (3) {\AA}, and β = 100.11 (3)° with V= 2268.2 (3) {\AA}3 and Z = 4. The P-N bond distances are all similar and average 1.574 A. The P-C bond length is 1.820 A. and the Cl-P-C angle was found to be 102.4°. The reaction between high molecular weight poly(dichlorophosphazene), (NPCl2)n, and methyl- or phenyl-1-lithio-o-carborane was also studied. Chlorine substitution is a slow process, and is accompanied by chain cleavage. The nucleophilic replacement of the halogen atoms yielded high polymers of structure IX that contain up to 15{\%} of the side groups as carboranyl units. The remaining chlorine atoms were replaced by treatment with sodium trifluoroethoxide. The properties and structure of the macromolecules are discussed.",
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Synthesis and Structure of Carborane-Substituted Cyclic and Polymeric Phosphazenes. / Allcock, Harry R.; Scopelianos, A. G.; O'Brien, J. P.; Bernheim, M. Y.

In: Journal of the American Chemical Society, Vol. 103, No. 2, 01.01.1981, p. 350-357.

Research output: Contribution to journalArticle

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N2 - The synthesis of the first carborane-substituted cyclophosphazenes together with the preparation, by two different approaches, of the first carborane-substituted phosphazene linear polymers is reported. The cyclic derivatives IV are both precursors and model compounds for the analogous polymeric derivatives VI. The crystal and molecular structure of IV (R = phenyl) has been investigated by single-crystal X-ray diffraction techniques. The molecule contains a planar phosphazene trimer ring bound directly to the phenyl carboranyl group through a P-C bond. The absence of steric and electronic influences by the phosphazene and carboranyl units on each other is discussed. The crystals of IV (R = phenyl) are monoclinic with the space group P21/n and with a = 9.476 (3) Å, b = 12.984 (2) Å, c = 18.726 (3) Å, and β = 100.11 (3)° with V= 2268.2 (3) Å3 and Z = 4. The P-N bond distances are all similar and average 1.574 A. The P-C bond length is 1.820 A. and the Cl-P-C angle was found to be 102.4°. The reaction between high molecular weight poly(dichlorophosphazene), (NPCl2)n, and methyl- or phenyl-1-lithio-o-carborane was also studied. Chlorine substitution is a slow process, and is accompanied by chain cleavage. The nucleophilic replacement of the halogen atoms yielded high polymers of structure IX that contain up to 15% of the side groups as carboranyl units. The remaining chlorine atoms were replaced by treatment with sodium trifluoroethoxide. The properties and structure of the macromolecules are discussed.

AB - The synthesis of the first carborane-substituted cyclophosphazenes together with the preparation, by two different approaches, of the first carborane-substituted phosphazene linear polymers is reported. The cyclic derivatives IV are both precursors and model compounds for the analogous polymeric derivatives VI. The crystal and molecular structure of IV (R = phenyl) has been investigated by single-crystal X-ray diffraction techniques. The molecule contains a planar phosphazene trimer ring bound directly to the phenyl carboranyl group through a P-C bond. The absence of steric and electronic influences by the phosphazene and carboranyl units on each other is discussed. The crystals of IV (R = phenyl) are monoclinic with the space group P21/n and with a = 9.476 (3) Å, b = 12.984 (2) Å, c = 18.726 (3) Å, and β = 100.11 (3)° with V= 2268.2 (3) Å3 and Z = 4. The P-N bond distances are all similar and average 1.574 A. The P-C bond length is 1.820 A. and the Cl-P-C angle was found to be 102.4°. The reaction between high molecular weight poly(dichlorophosphazene), (NPCl2)n, and methyl- or phenyl-1-lithio-o-carborane was also studied. Chlorine substitution is a slow process, and is accompanied by chain cleavage. The nucleophilic replacement of the halogen atoms yielded high polymers of structure IX that contain up to 15% of the side groups as carboranyl units. The remaining chlorine atoms were replaced by treatment with sodium trifluoroethoxide. The properties and structure of the macromolecules are discussed.

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